JPS60126645A - Direct positive silver halide photosensitive material and method for processing it - Google Patents

Abstract

PURPOSE:To control repeating reversal due to exposure, and to lower the Dmin by incorporating a tetrazolium compd. in an emulsion layer contg. silver chloride in a specified ratio or more or another hydrophilic colloidal layer, and adding a specified compd. to the developing soln. of this photosensitive material. CONSTITUTION:A direct positive silver halide emulsion layer on a hydrophilic colloidal layer located on the same side of a support as the emulsion layer incorporates a tetrazolium salt represented by formula I or II in which R2-R4, R11-R14 are each optionally substd. alkyl, aryl, phenyl, heterocyclic, or the like; X<-> is an anion; D is a bivalent aromatic group, or the like; and (m) is 1 or 2. The developing soln. of this photosensitive material contains a compd. represented by formula III in which Y is NO or methine; Z is N or imino; V is H or SH; at least one of Y and Z is N and when Y is methine, W is imino; (n) is 0 or 1; when Z is C, N is 1; and R1 is H or lower alkyl, halogen, or NO2. As a result, repetition of reversal due to exposure is prevented and a high-contrast image is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a direct positive silver halide photographic material for aesthetic effects. The present invention relates to a direct positive halogenated photosensitive material that eliminates fog and produces a positive image, and a developing method thereof.

(Prior art) A light source rich in ultraviolet light, such as xenon, metal halide,
When manufacturing a direct positive silver halide photographic light-sensitive material using a mercury lamp, tank high-pressure mercury lamp, etc. for exposure, as a type of light-sensitive material that can be handled under a safe source fluorescent lamp that has been cut off from ultraviolet light, Since the reversal sensitivity of the photosensitive dye decreases and becomes close to the re-inversion sensitivity, there is a strong tendency for re-inversion to occur in practice.

This tendency for re-inversion to occur is particularly strong when silver halide containing a large amount of silver chloride is used.

However, in order to improve this, it is necessary to increase the silver bromide content of silver halide.

However, this improved method has the disadvantage that as the silver bromide content increases, the gradation tends to become duller and satisfactory photographic performance cannot be obtained.

In particular, these drawbacks become noticeable when processing with super-additive developing agents (phenidone or metholone). This reduces work efficiency when using positive silver halide photosensitive materials.

(Object of the Invention) The object of the present invention is to suppress re-inversion (by exposure), and to
The object of the present invention is to provide a direct positive silver halide photographic photosensitive compound with low in and high contrast.

A further object of the present invention is to provide direct positive silver halide photographic photosensitive phase processing and its processing method, which can be processed with a rapid processing developer and still provide photographic properties with low IIIin, high contrast, and so-called clarity. It is in.

(Structure of the Invention) The above-mentioned object of the present invention is to provide on a support at least one direct positive silver halide emulsion layer having a silver halide composition of 50 mol % or more containing silver chloride; A direct positive halide photosensitive material containing a tetrazolium compound in an emulsion layer and/or at least one hydrophilic colloid layer on the same side of the emulsion layer and the support, and the above-mentioned photosensitive layer are described below. This can be achieved by a treatment method of treating with a dispersion containing at least one compound represented by the general formula [I].

General formula [■ Co, where Y is a hydrogen atom or a methine group, 2 is a hydrogen atom or a carbon atom, W is a sulfur atom, an oxygen atom, or an imino group, and V is a hydrogen atom or a mercapto group. . However, when Y and 2 are a small 1 ((both are nitrogen atoms, when Y represents a methine group, W is an imino group, n is O or], and when 2 is a hydrogen atom n is O
, where 2 is a carbon atom, n is 1. R3 is a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group.

The present invention will be explained in more detail below.

In the direct positive silver halide photographic photosensitive phase forming of the present invention (hereinafter simply referred to as the photosensitive phase forming of the present invention and 1μ top), in a hydrophilic colloid layer provided on a support, 7') a lazolium compound and 5
It is characterized by a structure in which silver halide containing 0 mol % or more of silver chloride is contained in the same layer or in separate layers.

In the present invention, the above-mentioned tetrazolium compound contained in the hydrophilic colloid layer preferably has the following general formula ['[
I] to [VI].

- General formula [■ General formula [1■] The above general formula [11] to [At the V opening, R2-R18
are substituted or non-@ substituted alkyl groups (e.g., methyl group, ethyl group, propyl group, tθrt-butyl group, etc.), allyl groups, phenyl groups (e.g., phenyl group, tolyl group, hydroxyphenyl group, alkoxyphenyl group,
carboxyphenyl group, alkoxycarbonylphenyl group, minophenyl group, mercaptophenyl group, sulfoxyphenyl group, aminosulfoxyphenyl group, nitrophenyl group, halogenated phenyl group, etc.), naphthyl group (e.g. α-naphthyl group, β-su7tyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.) and heterocyclic groups (such as thiazolyl group, benzothiazolyl group, oxacylyl group, pyrimidine group, pyridyl group, pyrazolyl group, etc.) Represents a selected group, any of which may be a group capable of forming a metal chelate or complex.

In addition to R4, R4, R+o, R□, and R54&''L, it may be a hydroxy group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a mercapto group, an alkoxysulfide group, or a cyano group.

X■ represents an anion, and may be any generally known anion.

D represents a divalent aromatic group such as a phenylene group, and E represents a divalent group selected from an alkylene group, an aralkylene group, and an aralkylene group.

m represents 1 or 2. However, if the compound is R4゜R2
In the case where an inner salt is formed with R8°, m is l.

Examples of the anion represented by xQ in the tetrazolium compound of the present invention include chloride ion, bromide ion,
Halogen ions such as iodide ions, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, acid groups of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-)luenesulfonic acid. Lower alkylbenzenesulfonic acid anions such as anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, investigative thread anions such as tetraphenylboron, etc. Dialkyl sulfosuccinate anion such as ethylhexyl sulfosuccinate anion, polyether alcohol sulfate ester anion such as cetyl polyethenoxysal 7ate anion, stearate anion '4 (') Higher Bi fatty acid anion, polyacrylic acid Examples include polymers such as anions with acid groups attached.

Specific compound examples of the tetrazolium compound used in the present invention are shown below, but the compounds that can be used in the present invention are not necessarily limited to these.

(Compound examples) (1) 1,5-dimethyl-4-phenyl-IH-tetrazolium chloride (2) 1,5-dimethyl-4-(3,4-xylylnotetrazolium chloride (3) 5-hydroxy-1, 3-bis(n-nitrophenylno-1)1-chloride f4) 1,3,5-tri(p-calphokidiethylphenyl-IH-tetrazolium chloride (5) l-(benzthiazol-2-ylno-3-phenyl) -5-(0-chlorophenyl)-2H-detrazolium bromide (6) 4,5-dimethyl-1-phenyl-IH-tetrazolium chloride (7) 415-dimethyl-1-(3,4-xy1norph -IH-tetrazolium chloride (s) 3-(p-hydroxyphenyl)-5-methyl-
1-Phenyl-IH-tetrazolium bromide (9) 1.3-diphenyl-5-ethyl-IH-tetrazolium bromide C1o) 1*”-diphenyl-5-n-hexyl-
IH-tetrazolium bromide (11) 5-cyano-1,3-diphenyl-IH-tetrazolium bromide (12) l, 4.5- )-5-(4
-chlorophenyl)-3-C4-nitrophenyl)-1
H-tetrazoliumchloride (14) 5-hydroxy-1,3-diphenyl-IH-tetrazoliumhydroxide inner salt (L5J 5-terazocetyl-1,3-di(p-ethoxyphenyl)-1H- Tetrazolium bromide (16Jl,
5-diphenyl-3-(p-trirunow LH-tetrazolium chloride (], 7) 1 , 5-diphenyl-3-(p-iodophenyl)-1H-tetrazolium chloride (1B),
1.3-diphenyl-5-(p-diphenylno 11(
-Tetrazolium chloride (19) 5-[p-(p-acetamido-nilinonophenyl)-1,4-dimethyl-IH-tetrazolium chloride (21:J) 5- (p-dimethylminostyril)
-4-ethyl-1-phenyl-IH-tetrazolium chloride (21) 3.5-diallyl-1-(tetrazole-5-
Iruno IH-tetrazolium chloride (22J l-
Cyclohexyl-4,5-dimethyl-IH-tetrazolium chloride (23) 3-(p-acetamidophenyl)-1,
5-Diphenyl-IH-tetrazolium bromide (2S5-recetyl-1,3-diphenyl-IH-tetrazolium bromide (25) 1-(ro-chlorophenyl)-4,5-
Dimethyl-IH-tetrazolium chloride (26) 1-cyclohexyl-4,5-dimethyl-I
H-tetrazolium chloride (27) 1- (0-chlorophenyl)-'+ 5-
Dimethyl-IH-tetrazolium chloride (28) 1-(p-bromophenyl)4,5-dimethyl-IH-tetrazolium chloride (2IJ) 4,5-dimethyl-1-p-,)lyluIH-tetrazolium chloride (30) 2-(pendithiazol-2-ylno-3-phenyl-5-dotecyl-2H-tetrazolium bromide)
Do(31) 2.3-diphenyl-5-(4-t-octyloxyphenyl)-2H-tetrazolium chloride (32) 2.3.5-Triphenyl-2H-tetrazolium chloride (33) 2,3. 5-)su(p-cal4mixyethylphenyl-2E-tetrazolium-2,2-di1tylhexylsuccinate (34)2-(benzothiazole-2-inoley3-
Phenyl-5-(0-chlorophenyl)-2H-tetrazolium chloride (35) 2,3-diphenyl-2H-tetrazo+51 nm chloride (36) 2,3-diphenyl-5-methyl-2H-
Tetrazolium chloride (37) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium chloride (38-2,3-diphenyl-5-ethyl-211-tetrazolium chloride (39) 2,3 -diphenyl-5-n-hexyl-2H
-Tetrazolium chloride.

(40) 5-cyano-2,3-diphenyl-2H-tetrazolium diisoprobylna 7talenesulfonate (ax) 2- (pendithiazol-2-yl)-3-
Phenyl-3-(4-)lyl)-2H-tetrazolium chloride (42) 2-(benzothiazol-2-yl)-5
-(4-chlorophenyl)-3-(4-nitrophenyl) -2H-tetrazolium chloride (43) 5-ethoxycarbonyl-2,3-di(3-nitrophenyl)
-2H-tetrazolium-1-methyl-benztriazole sulfonate (44) 5-7cetyl-2,3-di(p-ethoxyphenylno-2H-tetrazolium chloride (4-2,5-diphenyl-3-( p-) Cournot 2H-tetrazolium-2-mercaptobenzoxazole sulfonate (46) 2.5-diphenyl-3-(p-iodophenylno 2H-tetrazolium chloride (47) 2.3-
Diphenyl-5-(p-diphenyl-2H-tetrazolium chloride C48) 5-(p-bromophenyl)-2-phenyl-3-(2,4,6-)lichlorophenyl]-2H-
Tetrazolium chloride<49) s-(p-hydroxyphenyl)-5-
Cp-nitrophenylJ-2-phenyl+ 2H-tetrazolium chloride (5o)5-(3+'-dimethoxyphenyl)-3-(
2-Ethoxyphenyl-2-(p-methoxyphenyl)-2H-tetrazolium chloride (51J 5- (
4-cya/phenyl)-2,3-diphe-2H-tetrazolium chloride (52) 3-(p-clovetrimidophenyl)-2,5-diphenyl-2H-tetrazolium chloride (53) 5-acetyl-2 , 3-diphenyl-2H-tetrazolium chloride (5425-(fluor-2-yl)-2,3-di7-diru-2H-tetrazolium chloride (55) 5 Q (Checy 2-yl)-'g+ 3
-Sifale-2H-tetrazolium chloride (5S2,3-diphenyl-5-(quinol-2-yl)-2H-tetrazolium chloride (57J2,3-diphenyl-15-(benzoxazol-2-yl)-
2H-Tetrazolium chloride The tetrazolium compound used in the present invention is described in, for example, Chemical Reviews.
) Volume 55, pages 335-483.

The tetrazolium compounds used in the present invention can obtain preferable properties when used alone, but the preferable properties will not deteriorate even when a plurality of them are combined in any ratio.

One preferred embodiment of the present invention is to add the tetrazolium compound of the present invention to a silver halide emulsion layer. In another preferred embodiment of the present invention, it is added to a hydrophilic colloid layer that is in direct instant contact with a hydrophilic colloid layer containing a silver halide emulsion layer, or to an adjacent hydrophilic floid layer via an intermediate layer.

In another embodiment, the tetrazolium compound of the present invention is dissolved in a suitable solvent such as alcohols such as methanol and ethanol, ethers, esters, etc., and applied to the outermost layer of a photosensitive material by an overcoating method or the like. It may be contained in the photosensitive material of the present invention by directly coating the area where the photosensitive material will be.

The tetrazolium compound used in the present invention is 1×10 per mole of silver halide contained in the photosensitive layer composition of the present invention.
From molar to 5×10 molar, particularly preferred.

The silver halide used in the light-sensitive material of the present invention includes silver chloride, silver chlorobromide, silver chloroiodide, and silver chloroiodide, and in any case, silver chloride is contained in an amount of 50 mol% or more. However, if the agglomerated silver content is less than 50 mol %, the high contrast effect of the present invention will be lost, which is not preferable.

The silver halide emulsion containing 50 mol % or more of the above-mentioned chloride according to the present invention may be prepared by a commonly known method such as an acidic method, a neutral method, or an ammonia method, for example by simultaneous mixing. It can be produced by a method such as a method, a back mixing method or a forward mixing method, and optionally an additive stream W.
, pH or EAg can also be controlled.

Although the silver halide contained in the silver halide emulsion layer of the present invention is not limited to
．． 05 to 1.5 microns, preferably 01 to 0.5 microns, with at least 75%, preferably 80% or more of the total particle number being 05 to 1.5 times the average particle size;
Preferably, it is desirable to include silver halide having a grain size of 0.6 to 1.4 times.

A most preferred embodiment of the present invention is that the silver halide of the present invention has an average grain size of 0.10 NO, 3μ, and more than 80% of all grains have an average grain size of It is a powdered silver bromide with a grain size of 0.6 to 14 times that of silver bromide.

An organic desensitizer can be added to the silver halide emulsion layer according to the present invention. υ: (Fluorene fatty conductor having a nitro group described in No. 49-84432, compound having nitrophenylmercapto 4 described in JP-A No. 49-8463"tU, US 0.
10 Patent No. 2,669,515, pinacryptol yellow, 5-m-nitrobenzyritene rhodanine, etc.5. The addition fit of these organic molecular weight reducing agents is 1.0 x 10 moles per 1 mole of halogenide. ○×10 mole range
;, preferably, <f;t 1. OX 10-all 1.0
Xlo moles.

In addition, the above-mentioned halogenated (,1 (iridium, rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron, t4K, -11
1i Lead, lead, etc. atoms may be contained. When these atoms are contained, they may be of the surface latent image type per mole of silver halide or may be of the internal type.Furthermore, silver halide prepared by various methods may be used. The crystal shape may be a cube, an octahedron, or a devised shape, and is not limited to any of the shapes.

The direct positive silver halide used in the present invention is fogged by conventionally known techniques before exposure. The burr may be imparted using a reducing agent alone or in combination with a reducing agent and a gold compound. Representative such useful reducing agents include, for example, formalin, hydrazine, polyamines (e.g., triethylenetetramine, tetraethylenebencumin, etc.), thio crude dioxide, tetra(hydroxymethylnophosphonium chloride, boron Compounds (for example,
Contains amine borane, sodium borohydride, etc., stannous chloride, etc., and generally per mole of silver halide, z,
ox1o4 to 2.0XIO mole) i. In particular, polyamine thiourea dioxide and boron compounds are preferably used. In addition, typical examples of the above gold compounds include G co, chloroauric acid, potassium chloroaurate, sulfur compounds,
It includes selenium compounds and the like, and is generally used in an amount of 1.0X10 to 1.0Xlo mol per mol of silver halide.

The degree of fog imparted to the direct positive silver halide of the present invention can be suitably selected depending on the color of the fogging agent, the flow rate of fogging ripening, and the time conditions.

The silver halide and tetrazolium arsenide of the present invention are contained in the hydrophilic colloid layer. The hydrophilic colloid particularly advantageously used in the present invention is gelatin, but hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic, alkyl acids, hydrolyzed cellulose acetate, acrylic acid, etc. , imidized holamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin #l, conductor,
For example, U.S. Patent Nos. 2,614,982 and 2,52
Phenylcarbamyl gelatin, sylated gelatin, phthalated gelatin as described in the specifications of No. 5,753, or U.S. Pat. No. 2,548,520, U.S. Pat. Examples include those obtained by graft polymerizing gelatin with a monoht compound having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in Akira I11. These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, haze layers, intermediate layers, etc.

The photosensitive material of the present invention is obtained by coating a hydrophilic colloid layer containing the silver halide and tetrazolium compound mentioned in the present invention on a suitable photographic support. Typical examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyester films, polypropylene films, polycarbonate films, polystyrene films, etc. Each of these supports is coated with at least one hydrophilic colloid layer containing a silver halide or a tetrazolium compound selected as appropriate depending on the intended use of the light-sensitive material. However, the photosensitive material of the present invention has a retention layer having an appropriate thickness, that is, preferably 0.000.
It is desirable that the gelatin protective layer has a thickness of 1 to 0 μm, particularly preferably 0.8 to 2 μm.

The hydrophilic colloid used in the present invention may optionally contain various photographic additives, such as Seratin N plasticizer, hardening agent, surfactant, recording stabilizer, ultraviolet absorber, anti-staining agent, pH adjuster, antioxidant, antistatic agent, thickener, grain propensity agent, dye, mordant, brightener, development speed control! A matting agent or the like can be used in the pronation without impairing the effect of the present invention.

The various additives mentioned above can be particularly preferably used in the present invention, such as thickeners or plasticizers, such as those described in U.S. Pat. -4939 Publication, West Germany Exit 1 Publication No. 1,90
Specification of No. 4,604 (, Japanese Publication No. 48-6371.5,
Glaze Publication No. 45-15462/Pelky National Patent No. 76
No. 2,833, U.S. Time^'1, No. 3,767,410, Pelky National Registration * Substances described in each specification of G'r No. 558.143, such as styrene-sodium maleate. middle union, text lansulfue), etc., M
M! J agents include aldehyde-based, epoxy-based, ethyleneimine thread, active halogen-based, vinyl 8, sulfonyl 1,
Various hardeners such as isocyanate threads, Nisder sulfonate series, carbodiimide series, mucochloric acid series, acyloyl series, etc., and ultraviolet absorbers include, for example, U.S. Patent No. 3,253.
, 921 and British Patent No. 1,309,349, particularly 2-(2'-hydroxy-5-tertiary butylphenylumpenzotriazole, 2-(21-hydroxy -3', 5'-di-tertiary butylphenylnobenzotriazole, 2-(2'-hydroxy-3'-tertiary butyl-5'-butylphenyl-5-chlorobenzotriazole, 2-(2'-hydroxy) -31,51-di-tertiary butylphenyl-5-chlorobenzotriazole, etc., and dyes include U.S. Pat. No. 2,072,908 and German Patent No. 10 'i', 990. No. 3.048, U.S. Patent No. 3.048.
, 487, US Pat. No. 515,998, etc., may be used, and these compounds may be incorporated into protective layers, emulsion layers, interlayers, etc.

Furthermore, British Patent No. 548,532 describes coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials. , same No. 1,216,389
No. 3,026,202, U.S. '49 No. 3,5.
Specifications of No. 14,293, Special Publication No. 44-26580, No. 43-17922, No. 43-17926, No. 4
Publications No. 3-431.66 and No. 4B-2Q785,
French Patent No. 202,588, Belgian Patent No. 77
Anionic, cationic, nonionic, or amphoteric compounds described in the specifications of No. 3,459, JP-A-48-101118, etc. can be used.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24158,
9, De-Kokai No. 48-89979 σ) Publications, specifications of U.S. Pat. 1
No. 30, No. 48-90391, Special Publication No. 46-2415
No. 9, No. 46-39312, No. 48-438Q9,
Patent No. 111j', 47-83627 +3, etc. Compounds described in GJ [2], Matt matting agents include, for example, British Patent No. 1,221,980, U.S. Patent No. 2,992,101. No. 2,956,884,
French patent No. 1. : Compounds described in each specification of No. 395,544, Japanese Patent Publication No. 48-43125, etc., especially silica gel having a particle size of 05 to 20 μm, 05 to 20 μm
Examples include polymers of polymethyl methacrylate having a particle size of .

The emulsion layer and other constituent layers in the light-sensitive material of the present invention can be coated by various known coating methods. Coating methods include dipping armpit coating, air knife coating, roller coating, curtain coating, and extrusion 7 coating. The method described in US Pat. No. 2,681,294 is an advantageous method. Also, U.S. Patent No. 2,76
Two or more layers may be applied simultaneously using methods such as those described in U.S. Pat. No. 1,791 and U.S. Pat.

The light-sensitive material of the present invention is processed with a developer containing at least one compound represented by the following general formula [I].

General Formula [I] In the formula, Y is a nitrogen atom or a methine group, 2 is a nitrogen atom or a carbon atom, W is a sulfur atom, an oxygen atom or an imino group, and V is a hydrogen atom or a mercapto group. However, at least one of Y and 2 is a nitrogen atom, and when Y represents a methine group, W is an imino group. n
is 0 or l; when 2 is a nitrogen atom, n is O; when 2 is a carbon atom, n is l. R+ is a hydrogen atom,
A lower alkyl group, a halogen atom or a nitro group.

Typical specific examples of the compounds represented by the above general formula [I] are shown below, but the present invention is not limited to the use of these compounds.

(Compound Example 2 (a-1) Benzotriazole (a-2) 4-methylbenzotriazole (a-3)
5-bromobenzotriazole (a, -4) 5-nitrobenzotriazole (a-5) 5-ethylbenzotriazole (a-6) benzimidazole (a-1) 5-chlorobenzimidazole (a-8) 5
-Nitrointazole (a-9) 6-nitroindazole (a-10) 5-methylbenzointazole The compound represented by the above general formula [I] is generally known as a development inhibitor, The preferred amount of these development inhibitors used is 10 to 10 mobs per 11 parts of the developer solution.

In particular, it is preferable that the amount is 10 to lomol per developer 11I.

Further, it is preferable that the development inhibitor is dissolved in alkanolamine and/or glycol before being added to the developer.

In the method of processing a direct positive photographic light-sensitive material of the present invention, examples of the developer contained in the developer include the following: )10-(0R=OH)n-OK type developer includes catechol and pyrogallol. and its derivatives and ascorbic acid, representative examples include hydroquinone, tetrahydroquinone, bromohydroquinone, isopropylhydroquinone, tornohydroquinone, methylhydroquinone, z,3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3 -Jib 0 Mohydroki/
N, 2,5-dihydroxyaceto 7/N, 2.5-
Diethylhydroquinone, 2,5-di-p-7enethylhydroquinone, 2,5-dibenzoyl7minohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4 -acetyl-biloga-quart, 4(
2-hydroxybenzoylribirogallol, sodium ascorbic acid, etc.

HO-(0H=GH)n-NH, type peek, #! Typical agents include melt and loose aminophenol or aminovirazolonka, such as 4-aminephenol, 2-amino-6-phenylphenol, 2-amino-6-phenylphenol, lower 6-phenylphenol, 4-aminophenol, 2-amino-6-phenylphenol, -ami/-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4-dimethylsorcinol, zlj, 6-) diaminophenol, N-
Methyl-p-7minophenol, N-β-hydroxyethyl-p-minophenol, p-hydroxypheniH
,N-(0=O)! , -N horse type developer, for example, 4-ryominnow 2-methyl-N,N-digotylaniline,
2,4-Di-Ryo Minnow N, N-Diethyl Ryoji! jn, N-
(4-Ryomi/-3-methylphenylfumorpholine, p
-Phenylenediamine, 4-amino-N, N-dimethyl-3-hydrogeniline, N, N, H', N'-
Tetramethylbaraphenylenediamine, 4-remi/-N
-ethyl-N-(β-hydroxyethyl-N-7-niline,
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethylnoaniline, 4-amino-3-methyl-N-ethyl-N-
(β-methoxyethyl)-3-methyl-reniline, 4-
3-methyl-N-ethyl-N-(β-methylsulfone, 4-amino-N-butyl-N-γ-sulfobutylaniline, 1-(4-minophenylnobilidine, 6) -amino-]-ethyl, 1
．． ．． 2,3.4-tetrahydroquinoline, 9-ryominoideurolidine, etc.

Het I: I ring type fA imaging agent, for example, l-phenyl-3-pyrazolidone (phenidone J4,4'-dimethyl-1-phenyl
-Phenyl-4-amino-5-pyrazolone, 1- (p
-minophenyl)-3-7 minnow 2-pyrazoline, 1
-Phenyl-3-methyl-4-methyl-5-pyrazolone, 5-aminouracil, 5-amino-2,4,6-doryhydroxyphyrimidene, etc.

Other books include The Theory of the Photographic Process, 4th edition, by T. H. James.
ry of the, Photographic Pr
ocess, 'Fourth Edition)
Nos. 291-334 g) and Di4"-Nal of the
American Chemical Society (Tournal)
of the American Chemical
5ociθty) Volume 73, Section 3100 (1,9
Developers such as those described in 5'i) or those described in the present invention can be effectively used in the present invention.

It is preferable to use these additives 1 alone or in combination of two or more, or in combination of two or more.

Preferred combination e) A combination of hydroquinone and phenidone or hydroquinone and dimezone,
C/F Doroquinone is 59-50g/l.

Further, phenidone or dimezone is preferably used in a range of 0.05 to 5 g/l. Furthermore, the effects of the present invention will not be impaired even if a preservative such as sodium sulfite, potassium acetate, or sulfite is used as a preservative in the developer used in the present invention. One feature of the present invention is that it can be punched. iSulfuric acid #! Minato Ai is 0.06-1
Gram ion/e is preferred. Furthermore, hydroxyamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as bromokali, metal ion scavengers such as ethylenediaminetetraacetic acid,
Development accelerators such as methanol, ethanol, pencil alfur, polyalkylene oxide, sodium alkylarylsulfone, natural saponins, If11 activators such as sugars or alkyl esters of the above compounds, glutaraldehyde, formalin, glyoxal, etc. It is optional to add a hardening agent, sulfuric acid, hardening agent, etc.

The pH value can be set arbitrarily between 9 and 12. From the viewpoint of stability and photographic performance, the pH value is 4; 1 pH of 10 to 11 > [FN
Or preferable.

The developing solution according to the present invention may optionally contain alkanolamines or glycols as an organic solvent.

Regarding the above alkanolamines, there are monoethanolamine, jetanolamine, triethanolamine, etc., which are preferable.
1/amine is used. The amount of these alkanolamines used is preferably 20 to 500 g per developer 11, and particularly preferably 60 to 300 g per developer If11.

The above glycols include &;1 ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-bentanediol, etc., and diethylene glycol is preferably used. Preferably, these glycols are used in an amount of 20 to 500 q per 1 part of the hB1 developer used, and particularly preferably 60 to 300 q per part of the developer.

The above alkanolamines and glycols may be used alone or in combination of two or more.

In the method for processing a direct positive photographic light-sensitive material of the present invention, processing can be carried out under various conditions. For example, the processing temperature is
The developing temperature is preferably 50°C or less, especially around 30°C.Also, it is common for the current development process to be completed within 3 minutes, but particularly preferably within 2 minutes for good results. often brings. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping, stabilizing, fixing, and if necessary, steps such as pre-hardening and neutralization, and these may be omitted as appropriate. Furthermore, these processes include so-called manual development processes such as plate development and frame development, roller development,
Mechanical development such as hanger development may be used.

The object of the present invention can be completely achieved by the photosensitive material of the present invention and the processing method thereof described in detail above. If the burn-in is evaluated, its appearance,
It has been found that printing plates with excellent halftone dot quality and good sharpness can be made by printing.

The present invention will be further described in detail with reference to Examples below.
Do 1. The technical scope of the present invention is not limited to the following examples, and various embodiments are possible.

Example 1 Enriched rhodium (RhCJ, .3H20) dissolved in a solution of salt 1 arsenic was added at a concentration of 3 per mole of silver halide.
× 10 mol of chloride 9 elJ emulsions with varying silver chloride contents as shown in 1H were prepared at 45°C.
It was prepared using the same H, 7γ method over 30 minutes at 1j41.

The emulsion prepared as above was salted and dispersed (11) to obtain a Sakae dispersion emulsion. To this monodisperse 'l': I agent, 10 μl of thiourea dimoxide per mole of silver halide was added, and the mixture was aged at 60°C for 60 minutes, followed by the addition of 3 μl of small auric acid per mole of silver halide. It was then aged at 60°C until the highest performance was achieved, causing fog and failure.

The fogged emulsion thus obtained was divided into five equal parts, and a coating solution formulation E was prepared as shown below.

Coating liquid E1 manufactured by Wi; one of the 5 equal emulsions was mixed with an inhibitor and 5-nitrobenzimidazole at a concentration of 1.7 mm per mole of silver halide. F,p
- Nitrophenol-di-phenyl 7-osphonium chloride, 1 g per mole of silver halide, 20% water of saponin as a coating aid, m&wo/' 4.0 g per mole of silver halide. q1 as an extender such as stylinic acid co-i (combined with halogen (5 g per 111 moles and hard H
cormorant! A final coating solution of 1.56 was prepared by adding formaldehyde and glyoxal as agents.

Preparation of coating solution E; Same as sand preparation for coating solution F, except that in addition to the El additive, an aqueous solution of exemplified compound (32) was added in an amount of 5 x 10' mol per mol of silver halide. 1.5 per mole
Finish it to 1 and IC! A coating solution was prepared.

Preparation of Coating Solution E: Same as Coating Solution E, or in place of Exemplified Compound (32), 5 x 10 moles of Exemplified Compound (Recognized) was added as a 1% methanol solution per 1 mole of silver halide. .

Preparation of Coating Solution E; Same as Coating Solution E, except that the same molar amount of Exemplified Compound (39) was added instead of Exemplified Compound (12) as a tetrazolium compound.

Preparation of coating solution E: Same as Rinfu solution E4, but the same mole amount of (45) as a tetrazolium compound was added instead of specific example (39).

Next, for emulsion +: The following P solution was prepared as a coating solution for peritoneum.

Preparation of P1 solution: Add υ11 of pure water IQ7 to 1 kg of Seratin, and add υ11 of pure water IQ7 to 1 kg of Seratin, and make the swelling d'+'
4 Fix Heat to 40°C, add 1% water bath solution of sodium diethylsulfosuccinate sulfonate as a coating aid to 31, filter dye and 12 to form 1 of the following structural formula f1.
0% aqueous solution 11 was added, and fine silica gel powder 40y with an average particle size of 4 μ was added as a matting agent by dispersing it in gelatin.
111! Formaldehyde was added as a film agent to obtain 201.

(filter dye f,) Next, a back coating liquid B1 was prepared as follows.

Preparation of electrolytic solution: Add 20 Il of pure water to gelatin first layer, heat it to 40°C after swelling, add p as an additive, add 800 cc of a 110% aqueous solution of the dye used in the solution, and add a thickener. Coating styrene-maleic acid copolymer as 16y1, adding 16g of dipropylnaphthalene-sodium disulfonate as an auxiliary agent, and finishing with λ-pure water to 3Q7.

Protective film liquid for back surface manufactured by i1!1: A P liquid was prepared in the same way as the preparation of the protective film liquid for emulsion, and P liquid was prepared by removing the dye f1 from the liquid.

Preparation of silver halide photographic photosensitive material: Coating liquid B for the back side and its protective film liquid P on the undercoated polyethylene prephthalate, and adding the amount of gelatin to the front cloth. 2 g/tri'' and the latter was 1 g/trt after simultaneous multi-layer coating, the emulsion coating solution and its protective film solution were applied on the opposite side in the same way, and the amount of silver was 3?/rn
: (Serachin Kukan 2y/ha), Yasukun Kei! The amount of Seratin applied was 1g/g. When applying, use a combination hardening agent of formaldehyde, mucochloric acid, and ethyleneimine for 6iJ! I! φ[7ta.

Each of the above test samples was printed using an ultraviolet table printer (oRaJIQ Seisakusho HMW-) using an ultra-high pressure mercury lamp as a light source.
215) using a step wedge, and separately using a halftone original with a blackening rate of about 50%, it was returned and printed, and exposed so that the blackening rate of the test sample was 50%. .

The exposed test sample was processed under the following processing conditions by applying a developer having the following formulation and a commercially available fixer to a roller conveyance type automatic processor (developer tank capacity: fit 4011).

When using the developer, a stock solution of 50Q of the following developer was dissolved in 500rne of pure water and the solution was raised to 14.

(Processing conditions) Development: Temperature: 30°C, fixing for 30 seconds, washing with water for 20 seconds; 20 seconds [Developer (Developer)] Potassium bromide 2.5I EDTA-2N & 1.9 Potassium sulfite (55% aqueous solution) 90ml Potassium carbonate 259 Hydroquinone 1 og 5-methylbenzotrizole 100 5-nitrobenzotrizole 100 1-phenyl-5-mercaptotetrazole 0 m9 5-nitroindazole 50 m2 1-phenyl-4-methyl-4-hydroxymethyl- 3
-Pyrazolidone 0.59 Diethylene I) Fur 609 Adjust pH to 106 with sodium hydroxide, and finish to 500 by adding water.

According to the above, iii! ! Sag 2 for proofreading the photosensitive material mounted on the
After printing on the 28th edition SPP with a 2KW metal halide lamp, it was further processed with PS edition automatic development tIA (using ``I-cla PS edition developer)'', and then re-inversion, missing dots, and sharpness were visually evaluated. However, the results shown in Table 1 were obtained.

The characteristic d'r value in the table! , and the parrots are as shown below.

A: Best B: Good C: Moderately inferior D: Inferior As is clear from the results shown in the above table, silver chloride mol%
samples of the present invention containing 50% or more and the tetrazolium compound according to the present invention (Sample Shop 6, 8, 9,
It can be seen that in samples 10.11 and 13), fine reversal was suppressed compared to the comparative samples, and an excellent finish with clear sharpness was obtained.

Example 2 A photosensitive layer was prepared in the same manner as in Example 1, except that the developer used in this example was 5-methylbenztrizol, 1-phenyl-5, which was used in Example 1 above. -In place of mercaptotetrazole and 5-nitroindazole, the compounds shown in Table 2 below were added according to the amounts shown in the table to prepare a liquid solution.

Next, the test sample 8 prepared in Step 1 was exposed to ultraviolet light (HMW-215, manufactured by ORO Manufacturing Co., Ltd.) using an ultra-high pressure water tank as a light source in the same manner as in Example 1. Next, development was performed using a developer containing the compounds shown in the table below.

Table 2 Evaluation of the sample after the development treatment was performed according to Example 1.

The results are shown in Table 3.

Table 3 As is clear from the above table, by using the developer containing the development inhibitor according to the present invention, re-inversion can be suppressed and a silver image with excellent halftone dot omission and sharpness can be obtained. I understand.

Example 3 An emulsion was prepared in the same manner as in Example 1 without the addition of rhodium chloride, and ripened to yield whole Capri. Divide this emulsion into 5 equal parts and follow the coating solution formulations E to E5 to i1! Manufactured. However, each cloth supply liquid should contain a desensitizer.

Then, 1 g of pinacryptol yellow was added as a methanol solution per 1 mole of z-J halide. Below are 11 actual colors example 1
When the images were evaluated after exposure and processing in the same manner as above, it was found that the sample using the emulsion containing all the tetrazolium compounds according to the present invention suppressed re-inversion and produced an excellent finish with clear sharpness. .

(Effects of the Invention) By using the photosensitive abrasive material of the present invention, the object of 1fiJ is achieved, and thereby halftone dot omission and image sharpness can be improved. stop.

Furthermore, the above effects are further enhanced by processing with a developer containing a compound represented by the general formula [I], which will be described in detail later.

Agent Yoshimi Kuwahara

Claims (2)

[Claims] (1) having on a support at least one direct positive silver halide emulsion layer having a silver halide composition with a silver chloride content of 50 mol % or more; A direct positive silver halide photographic light-sensitive material, characterized in that a tetrazolium compound is contained in at least one hydrophilic colloid layer on the same side of the support. (2) having at least one direct positive silver halide emulsion layer on a support having a silver halide composition with a silver chloride content of 50 mol % or more; a surface containing a tetrazolium compound in at least one of the hydrophilic cotetraid layers on the same side of the support;
Direct-positive halogenated photocopy I, characterized in that a contact-adhered silver halide photosensitive material is treated with a developer containing at least one compound represented by the following general formula CI]
re4ft, material processing method. General formula [I] In the formula, Y is a nitrogen atom or a methine group, 2 is a nitrogen atom or a carbon atom, W is a sulfur atom, an oxygen atom, or an imino group, and V is a hydrogen atom or a mercapto group. It is the basis. However, at least one of Y and 2 is a nitrogen atom, and when Y represents a methine group, W is an imino group. n is 0 or 1, n is 0 when 2 is a nitrogen atom, and n is 1 when 2 is a carbon atom. R is a hydrogen atom, a lower alkyl group, a halogen atom or a nitro group. ]